Compositions and methods of combatting arthropodal pests using phenylhydrozone derivatives

ABSTRACT

Certain ( Alpha -fluoroalkyl)benzoyl chloride phenylhydrozones have been found to be anthelmintics and active against arthropod pests. The benzoyl ring and the phenylhydrazone ring can be otherwise substituted with, for example, halogen, nitro, another Alpha -fluoroalkyl group, or an alkyl group.

United States Patent Kaugars Dec. 30, 1975 COMPOSITIONS AND METHODS OFCOMBATTING ARTHROPODAL PESTS USING PHENYLHYDROZONE DERIVATIVES [75]Inventor:

[73] I Assignee: The Upjohn Company, Kalamazoo,

Mich.

[22] Filed: July 13, 1970 [21] Appl. NO.: 54,620

Girts Kaugars, Kalamazoo, Mich.

[52] US. Cl. 424/327; 260/566 B [51] Int. CI. A0lN 9/20 [58] Field ofSearch 424/327; 260/566 B [56] References Cited UNITED STATES PATENTS3/1957 Warner et al. 260/566 B X 12/1957 Jaworski et al. 424/327 2/1966Urbschat et al. 424/327 X OTHER PUBLICATIONS Humphries et al., J. Chem.Soc., 127, pp.-1304l307 (1925). Jones et al., J. Org. Chem. 26, pp.228-232 (1961 Primary Examiner-Albert T. Meyers Assistant ExaminrAllenJ. Robinson Attorney, Agent, or Firm-Roman Saliwanchik; Carl A. Randles,Jr.

57 ABSTRACT I group, or an alkyl group.

17 Claims, No Drawings COMPOSITIONS AND METHODS OF COMBATTINGARTHROPODAL PESTS USING PIIENYLHYDROZONE DERIVATIVES SUMMARY OFINVENTION This invention pertains to new chemical compounds, a newmethod of combatting arthropod pests; and new anti-arthropodalformulations. The invention is more particularly directed to new(or-fluoroalkyl)benzoyl chloride phenylhydrazones, to new(a-fluoroalkyDben- 10 u zoic acid 2-phenylhydrazide intermediates, a newnew antl-arthropodel t q yb n oy method of mbatti th d pests using h newchloride phenylhydrazones of this invention are readily(oz-fluoroalkyl)benzoyl chloride phenylhydrazones, p ep y reactmgfiselefited yh nz and to new anti-arthropodal formulations comprising acld2-phenylhydraz1de with phosphorus pentachlothe new(or-fluoroalkyl)benzoyl chloride phenylhydra- 15 reacting l g, c p gzones. fluoroalkyl)benzoyl chloride (dichlorophosphinyl)- The certainnew insecticidal and miticidal '(aphenylhydrazone t p d e nng hflu0roalky1)benzoyl chloride phenylhydrazones of this slred (ayU ychloride p y y invention have the general structural formula 20 zon Tproc can e repr ented as follows:

a- F al kyl I O H H (Y) n l C-N-N 5 Step 1. l

G-F al l yl phenol -F a l kyl Cl H I l m C=N- Step 1. of the foregoingprocess proceeds when the (er-fluoroalkyl)benzoic acid 2-phenylhydrazidestarting (Y compound (compounds of Formula II, above) and the whereina'-F,,alkyl is an d-fluoroalkyl group of from 1 to 3 carbon atoms,inclusive; X is halogen (chlorine, bromine, iodine, and fluorine),nitro, alkyl of from 1 to 6 carbon atoms, inclusive, and a-F alkyl; Y isalkyl of from 1 to 6 carbon atoms, inclusive, a-F alkyl, halogen, andnitro; n is an integer 2 or 3, n is an integer 0 to 3,

inclusive; and m is an integer from 0 to 3, inclusive, the sum of n +mbeing not more than 5, the sum of carbon atoms in alkyl substituentsbeing not more than 15, there being no more than one nitro group in themole cule, and no more than two a-F alkyl groups on any one benzene ringor three total.

DETAILED DESCRIPTION OF THE INVENTION phosphorus pentachloride are mixedin the presence of a reaction medium at a temperature in the range ofabout 10C. up to about the boiling point of the reaction medium. Higherand lower temperatures can be .used, however. The reaction rate will bedecreased at .low temperatures, and a pressure vessel would be needed toeffect reaction temperatures above the boiling point at atmosphericpressure. In accordance with a preferred embodiment, the initialreaction mixture is heated.

' Appropriate reaction media include, for example, the chlorinatedhydrocarbon solvents, aliphatic or aromatic hydrocarbon solvents, andethers. Representa- 3 tive specific ones are carbon tetrachloride(preferred), methylene chloride, chloroform, 1,2-dichloroethylene,benzene, toluene, technical hexane, diethyl ether, and dioxane.

The process can be practiced without isolating the(a-fluoroalkyl)benzoyl chloride (dichlorophosphinyl)- phenylhydrazoneintermediate when three equivalents or more of phenol are added to theinitial reaction mixture after it has been cooled to about to 25 C. Thephenol reacts with the (a-fluoroalkyl)benzoyl chloride(dichlorophosphinyl)-phenylhydrazone intermediate to produce triphenylphosphate, and the desired (a-fluoroalkyl)benzoyl chloridephenylhydrazone is then recovered and purified by conventional methods.The solvent medium is removed by evaporation, and the desired product,is recovered by methods of physical separation, e.g., filtration fromthe residual triphenyl phosphate or by chromatographic techniques. Thecompound is purified by recrystallization.

The (a-fluoroalkyl)benzoic acid 2-phenylhydrazide starting compounds ofFormula 11 can be readily prepared by known methods. According to onemethod an (a-fluoroalkyl)benzoyl chloride or fluoride is reacted with aphenylhydrazine as described by J. Hausknecht, Chem. Ber. 22, p. 324(1889), and E. Bamberger and W. Pemsel, Chem. Ber. 36, p. 359 (1903).Another method is described in U.S. Pat. No. 2,912,461, issued Nov. 10,1959, that utilizes a benzoate ester and a phenylhydrazine. Stillanother method described by W. Autenrieth and G. Thomae, Chem. Ber. 57,p. 423 (1924) reacts a benzoic acid anhydride with a phenylhydrazine toproduce the corresponding benzoic acid phenylhydrazide. Example 1hereinafter illustrates a conventional method for making(a-fluoroalkyl)benzoic acid 2- phenylhydrazide starting compounds.

The new anti-arthropodal (a-fluoroalkyl)benzoy1 chloridephenylhydrazones of this invention (compounds according to Formula I)can also be prepared by chlorinating an (a-fluoroalkyl)benzaldehydephenylhydrazone. Chlorination of an (a-fluoroalkyl)benzaldehydephenylhydrazone can be accomplished as described by .l. E. Humphries, H.Humble and R. Evans, J. Chem. Soc. 127, p. 1304 (1925). But thischlorination is of limited usefulness when the starting(a-fluoroalkyl)benzaldehyde phenylhydrazone has unsubstituted activesites that will yield to chlorination at positions on thephenylhydrazone portion that are desired to remain unsubstituted in aparticular instance. Direct chlorination of (a-fluoroalkyl)benzaldehydephenylhydrazone is an effective way of producing (afluoroalkyl)-benzoy1chloride (2,4,6-trichlorophenyl)- hydrazone.

Still another method described by L. A. Jones, C. K. Hancock, and R. B.Seligman, J. Org. Chem. 26, p. 228 (1961) can be used. The describedmethod utilized a,a,a-trichlorotoluene and 2,4-dinitrophenylhydrazine toproduce benzoyl chloride (2,4-dinitrophenyl)hydrazone. The new compoundsof this invention can be prepared in the same manner.

EXAMPLE 1 Preparation of a,a,a-Trifluoro'-m-Toluoyl ChloridePhenylhydrazone Part A m-(Trifluoromethyl)benzoic acid Z-phenylhydrazideTo a cooled solution of 35.0 g. (0.323 mole) phenylhydrazine in 300 ml.pyridine at 4 to 9 C. was added 57.6 g. (0.300 mole)m-trifluoromethylbenzoyl fluoride. The reaction mixture was set aside atabout 25 C. for 6 days. It was then poured into water and the aqueousmixture was stirred until crystallization was completed. The crystalswere collected on a filter, washed with water, washed with 1 Nhydrochloric acid, and washed with water again before recrystallizationfrom aqueous ethanol. A further recrystallization from a mixture ofbenzene and technical hexane gave 72.3 g. (85.9% yield) ofm-(trifluoromethyl)benzoic acid 2- phenylhydrazide having a meltingpoint at 116 to 117.5 C. An analytical sample recrystallized from amixture of 100 ml. benzene and 150 ml. technical hexane hadsubstantially the same melting point.

Analysis: Calcd. for C H F N Oz C, 60.00; H, 3,96; F, 20.34; N, 10.00.Found: C, 60.40; H, 4.09; F,

Part B a,a,a-Trifluoro-m-toluoyl chloride phenylhydrazone To asuspension of21.86 g. (0.105 mole) phosphorus pentachloride in 200 ml.carbon tetrachloride was added 28.02 g. (0.100 mole)m-trifluoromethylbenzoic acid Z-phenylhydrazide (prepared in Part A,above). The resulting suspension was stirred continuously at about 25 C.until evolution of gas decreased. The mixture was then heated to thereflux temperature. The solution thus obtained was chilled in crushedice and 33 g. (0.350 mole) phenol in ml. carbon tetrachloride was added.After removing the carbon tetrachloride by evaporation at 30 C., thesolution of product in triphenylphosphate was set aside for 1 week at 4C. When the product did not separate out, the solution waspoured over a1.3 kg. column of silica gel. The product was eluted with a mixture of 1part benzene and 1 part technical hexane. After removing the solvents byevaporation there was obtained 27.88 g. (93.3% yield) ofa,a,a-trifluoro-m-toluoyl chloride phenylhydrazone as a yellow solid.Recrystallization from 75 ml. petroleum ether gave the desired purecompound having a melting point at 54 to 56 C.

Analysis: Calcd. for C H ClF N C, 56.29; H, 3.37; Cl, 11.87; F, 19.08;N, 9.38. Found: C, 56.75; H, 3.56; Cl, 11.78; F, 18.74; N, 9.61.

EXAMPLE 2 Following the procedure of Example 1, Part A, but substituting3-bromo-5-(trifluoromethyl)benzoyl fluoride,2-chloro-5-(trifluoromethyl)benzoyl fluoride,2-iodo-3-(trifluoromethyl)benzoyl fluoride,2-fluoro-5-(trifluoromethyl)benzoyl fluoride,4-methy1-3-(trifluoromethyl)benzoyl fluoride,3-ethyl-5-(trifluoromethyl)benzoyl fluoride,3-isopropyl-5-(trifluoromethyl)benzoyl fluoride,3-butyl-5-(trifluoromethyl)benzoyl fluoride,3-n-hexyl-5-(trifluoromethyl)benzoyl fluoride,p-(trifluoromethyl)benzoyl fluoride,

7 m-(trifluormethyl)benzoic acid 2-(4-met hyl-2-nitrophenyl)hydrazidem-(trifluoromethyl)benzoic acid Z-(p-trifluoromethyl)hydrazide form-(trifluoromethyl)benzoic acid 2-phenylhydrazide, there were prepared3-bromo-5-(trifluoromethyl)benzoyl chloride phenylhydrazone,2-chloro-5-(trifluoromethyl)benzoyl chloride phenylhydrazone,

2-iodo-3-(trifluoromethyl)benzoyl chloride phenylhydrazone,

2-fluoro-5-(trifluoromethyl)benzoyl chloride phenylhydrazone,

4-methyl-3-(trifluoromethyl)benzoyl chloride phenylhydrazone,3-ethyl-5-(trifluoromethyl)benzoyl chloride phenylhydrazone,3-isopropyl-5-(trifluoromethyl)benzoyl chloride phenylhydrazone,3-butyl-5-(trifluoromethyl)benzoyl chloride phenylhydrazone,

3-n-hexyl-5-(trifluoromethyl)benzoyl chloride phenylhydrazone,

p-(trifluoromethyl)benzoyl chloride phenylhydrazone,

o-(trifluoromethyl)benzoyl chloride phenylhydrazone,

3,5-di-(trifluoromethyl)benzoyl chloride phenylhydrazone,

3-nitro-4-(trifluoromethyl)benzoyl chloride phenylhydrazone,

4-nitro-2-(trifluoromethyl)benzoyl chloride phenylhydrazone,

m-( l l -difluoroethyl )benzoyl chloride phenylhydrazone,3,5-dimethyl-4-(trifluoromethyl)benzoyl chloride phenylhydrazone,2-chloro-6-methyl-4-(trifluoromethyl)benzoyl chloride phenylhydrazone,

m-( l, l -difluoropropyl)benzoyl chloride phenylhydrazone,

m-(trifluoromethyl)benzoyl chloride (p-bromophenyl)hydrazone,

m-(trifluoromethyl)benzoyl chloride (p-chlorophenyl)hydrazone,

m-(trifluoromethyl)benzoyl chloride (p-nitrophenyl)hydrazone,m-(trifluoromethyl)benzoyl chloride (2,4-diiodophenyl)hydrazone,

m-(trifluoromethyl)benzoyl chloride (p-ethylphenyl)hydrazone,

m-(trifluoromethyl)benzoyl chloride (p-n-hexylphenyl)hydrazone,

m-(trifluoromethyl)benzoyl chloride (p-isopropylphenyl)hydrazone,

m-(trifluoromethyl)benzoyl chloride (2-chloro-4- nitrophenyl)hydrazone,

m-(trifluoromethyl)benzoyl chloride (4-methyl-2- nitrophenyl)hydrazone,and m-(trifluoromethyl)benzoyl chloride(p-trifluoromethylphenyl)hydrazine, respectively.

EXAMPLE 5 Preparation of a,a,a-Trifluoro-m-toluoyl chloride(2,4-dibromophenyl)hydrazone To an ice-cold solution of 5.28 g. (0.0200mole) a,a,a-trifluoro-m-toluoyl chloride phenylhydrazone in 200 ml.carbon tetrachloride is added 10.8 g. (0.0675 mole) bromine dissolved in25 ml. carbon tetrachloride. The solution is heated at the refluxtemperature for 4 hrs., and then the carbon tetrachloride is removed byevaporation under reduced pressure. The residue thus obtained isrecrystallized from technical hexane to give the desireda,a,a-trifluoro-m-toluoyl chloride (2,4-dibromophenyl)hydrazone.

The new anti-arthropodal (a-fluoroalkyUbenzoyl chloride phenylhydrazonesof Formula I can be used as the pure compounds, suchas those describedin the Examples, or as technical grade compounds from commercialproduction; but for practical reasons, the compounds are preferablyformulated with a diluent carrier with or without adjuvants for useagainst arthropod pests. There are many different kinds of diluentcarriers suitable for the method and formulation embodiments of thisinvention. Dispersible carriers are commonly used in the art. Suchcarriers may or may not include adjuvants such as wetting agents,emulsifying agents, stickers, and other components that indirectlypromote efficacy.

For example, pesticidal formulations useful against arthropods whichbecome epidemic can be formulated as dusts, wettable powders,emulsifiable concentrates, aqueous dispersions, solutions and flowablecreams for application to a situs, animals, and foliage, seeds or otherparts of plants. Granular formulations can be prepared and applied tosoil or on other surfaces. Moreover, the new (a-fluoroalkyl)benzoylchloride phenylhydrazones of the invention can be the sole active agentin a formulation or other insecticidal, miticidal, fungicidal,virucidal, bactericidal, or synergistic components may be included.

The new (a-fluoroalkyhbenzoyl chloride phenylhydrazones can be readilyformulated as dusts by grinding a mixture of the compound and apulverulent carrier in the presence of each other. Grinding isconveniently accomplished in a ball mill, a hammermill, or by airblastmicronization. A suitable ultimate particle size is less than 60microns. Preferably, 95% of the particles are less than 50 microns, andabout are 5 to 20 microns. Dusts of that degree of comminution areconveniently free-flowing and can be applied to animals, inanimatematter, fruit trees, crop plants, and soil so as to effect thoroughdistribution and coverage. Dusts are particularly adapted foreffectively controlling insects and mites over wide areas when appliedby airplane. They are also indicated for application to the undersidesof plant foliage and to the skin of poultry and hairy animals.

Representative suitable pulverulent carriers include the natural clayssuch as China, Georgia, Barden, attapulgus, kaolin, and bentonite clays;minerals in their natural forms as they are obtained from the earth suchas talc, pyrophyllite, quartz, diatomaceous earth, fullers earth, chalk,sulfur, silica and silicates; chemically modified minerals such aswashed bentonite and colloidal silica; and organic flours such as wood,walnut shell, soybean, cottonseed, and tobacco flours, and free-flowing,hydrophobic starches.

Dusts can also be prepared by dissolving an (afluoroalkyl)benzoylchloride phenylhydrazone in a volatile solvent such as methylenechloride, mixing the solution with a pulverulent carrier and evaporatingthe solvent.'

The proportions of pulverulent carrier and (afluoroalkyl)benzoylchloride phenylhydrazone can vary over a wide range depending upon theinsects, spiders, ticks, or mites to be controlled and the conditions oftreatment. In general, dust formulations can contain up to about 90% (ona weight basis) of the active ingredient. Dusts having as little as0.001% of the active ingredient can be used, but a generally preferredproportion is from about 0.50% to about 20% of active ingredient.

The dispersible powder formulations of this invention are prepared byincorporating a surfactant in a dust formulation prepared as describedabove. When about 0.1% to about 12% of a surfactant is incorporated in adust, the dispersible powder thus obtained is particularly adapted forfurther admixture with water for spraying on inanimate matter andproducts, fruit trees, field crops, soil, and livestock. The dispersiblepowders can be admixed with water to obtain any desired concentration ofactive ingredient, and the mixture can be applied in amounts sufficientto obtain predetermined rates of application and uniform distribution.With this flexibility in mind, the dispersible powders of the inventioncan conveniently comprise preferably about 10 to about 80% of activeingredient.

thylenesorbitan monolaurate, alkyl aryl polyether sulfates, alkylarylpolyether alcohols, alkyl naphthalene sulfonates, alkyl quaternaryammonium salts, sulfated fatty acids and esters, sulfated fatty acidamides, glycerol mannitan laurate, polyalkylether condensates of fattyacids, lignin sulfonates, and the like. The preferred class ofsurfactants includes blends of sulfonated oils and polyalcoholcarboxylic acid esters (Emcol l-l-77), blends of polyoxyethylene ethersand oil-soluble sulfonates (Emcol l-I-400), blends of alkyl arylsulfonates and alkylphenoxy polyethoxy ethanols (Tritons X-l5l, X-l6l,X-l7l), e.g., about equal parts of sodium kerylbenzene sulfonate andisooctylphenoxy polyethoxyvethanol containing about l2 ethoxy groups,and blends of calcium alkyl aryl sulfonates and polyethoxylatedvegetable oils (Agrimul N 8). It will be understood, of course, that thesulfate and sulfonate surfactants suggested above will preferably beused in the form of their soluble salts, for example, their sodiumsalts. All of these surfactants are capable of reducing the surfacetension ofwater to less than about 40 dynes per centimeter inconcentrations of about 1% or less. The dispersible powder formulationscan be prepared with a'mixture of surfactants of the types indicated ifdesired.

A suitable dispersible powder formulation is obtained by blending andmilling 327 lbs. of Georgia Clay, 4.5 lbs. of isooctylphenoxy polyethoxyethanol (Triton X-l00)as a wetting agent, 9 lbs. of a polymerized sodiumsalt of substituted benzoid long-chain sulfonic acid (Daxad 27) as adispersing agent, and l 13 lbs. of the active ingredient. The resultingformulation has the following percentage composition (parts herein areby weight unless otherwise specified).

Active ingredient 25% isooctylphenoxy polyethoxy ethanol l% Polymerizedsodium salt of substituted benzoid longchain sulfonic acid 2% GeorgiaClay 72% This formulation, when dispersed in water at the rate of 10lbs. per gals, gives a spray formulation containing about 0.3% (3000ppm) active ingredient which can be applied to insects, spiders, ticks,or mites, plants or other arthropod habitats, or to their foods forcontrol of various arthropods.

If desired, dispersants such as methyl cellulose, polyvinyl alcohol,sodium ligninsulfonates, and the like can be included in the dispersiblepowder formulations of this invention. Adhesive or sticking agents suchas vegetable oils, naturally occurring gums, casein, and others can alsobe included. Corrosion inhibitors such as epichlorohydrin andanti-foaming agents such as stearic acid can also be included.

The anti-arthropodal new (a-fluoroalkyDbenzoyl chloride phenylhydrazonesof this invention can be applied to insects, spiders, ticks, mites,objects or situs in aqueous sprays without a solid carrier. Since, however, the compounds themselves are relatively insoluble in water theyare preferably dissolved in a suitable inert organic solvent carrier.Advantageously, the solvent carrier is immisciblewith water so that anemulsion of the solvent carrier in water can be prepared. If, forexample, a water-miscible solvent carrier such as ethanol is used thesolvent carrier will dissolve in the water and any excess(a-fluoroalkyl)benzoyl chloride phenylhydrazonev will be thrown out ofsolution. In an oil-in-water emulsion, the solvent phase is dispersed inthe water phase and the dispersed phase contains the active ingredient.In this way, uniform distribution of a water insoluble active ingredientis achieved in an aqueous spray. A solvent carrier in which(a-fluoroalkyl)benzoyl chloride phenylhydrazones are highly soluble isdesirable so that relatively high concentrations of active ingredientcan be obtained. Sometimes, one or more solvent carriers with or withouta cosolvent can be used in order to obtain concentrated solutions of theactive ingredient, the main consideration being to employ awater-immiscible solvent for the active ingredient that will hold thecompound in solution over the range of concentrations useful forapplying to insects, spiders, ticks, and mites.

The emulsifiable concentrates of the invention are prepared, therefore,by dissolving the active ingredient and a surfactant in a substantiallywater-immiscible solvent carrier (i.e., a solvent carrier which issoluble in water to the extent of less than 2.5% by volume attemperatures of the order of 20 to 30 C.), for example, cyclohexanone,methyl propyl ketone, summer oils, ethylene dichloride, aromatichydrocarbons such as benzene, toluene, and xylene, and high-boilingpetroleum hydrocarbons such as kerosene, diesel oil, and the like. Ifdesired, a cosolvent such as methyl ethyl ketone, acetone, isopropanol,and the like can be included with the solvent carrier in order toenhance the solubility of the active ingredient. Aqueous emulsions arethen prepared by mixing with water to give any desired concentration ofactive ingredient. The surfactants which can be employed in the aqueousemulsions 1 1 of the invention are those types noted above. Mixtures ofsurfactants can be employed, if desired.

Advantageously, the concentration of active ingredient in theemulsifiable concentrates can range from about 5% to about 50% byweight, preferably from about to about 40%. A concentrate comprising (byweight) of the compound dissolved in a waterimmiscible solvent of thekind noted above can be admixed with an aqueous medium in theproportions of 13 ml. of concentrate with 1 gal. of medium to give amixture containing 700 parts of active ingredient per million parts ofliquid carrier. Similarly, 1 qt. of a 20% concentrate mixed with 40gals. of water provides about 1200 ppm (parts per million) of activeingredient. In the same manner, more concentrated solutions of activeingredient can be prepared.

The concentrate formulations of the invention which are intended for usein the form of aqueous dispersions or emulsions can also comprise ahumectant, that is to say, an agent which will delay the drying of thecomposition in contact with material to which it has been applied.Suitable humectants include glycerol, diethylene glycol, solubilizedlignins, such as calcium ligninsulfonate, and the like.

The granular formulations of this invention are convenient forapplication to soil when persistence is desired. Granulars are readilyapplied broadcast or by localized, e.g., in-the-run applications. Theindividual granules may be any desired size from 10 to 60 mesh,advantageously 20 to 40 mesh. Granulars are prepared by dissolving theactive compound in a solvent such as methylene chloride, xylene, oracetone and applying the solution to a quantity of a granulatedabsorbent carrier. Representative granulated absorbent carriers includeground corn cobs, ground walnut shells, ground peanut hulls, and thelike. If desired, the impregnated granulated absorbent carrier can becoated with a coating that will preserve the integrity of the granularuntil it is applied to an object or situs favorable for release of theactive ingredient.

The rates of application to insects, spiders, ticks, mites, objects, orsitus will depend upon the species of arthropod to be controlled, thepresence or absence of desirable living organisms, temperatureconditions of treatment, and the method and efficiency of application.In general, arthropocidal activity is obtained when the compounds areapplied at concentrations of about 10 to about 6000 ppm, preferable atconcentrations of about to about 4000 ppm.

The formulations containing new (a-fluoroalkyl)- benzoyl chloridephenylhydrazones according to the invention, can be applied to insects,spiders, ticks, mites, objects or situs by conventional methods. Forexample, an area of soil, a building, or plants can be treated byspraying wettable powder suspensions, emulsions, or solutions from powersprayers or from hand-operated knapsack sprayers. Dips can be used forlivestock. Dusts can be applied by power dusters, or by 12 hand-operateddusters. Creams and ointment formulations can be applied to skin orobjects for prolonged protection from insects, spiders, ticks, or mites.

The active compounds of the invention can also be formulated inrelatively dilute proportions in a dispersible insecticide carrier forhousehold applications. Thus, the active compounds can be formulated industs having from about 0.1 to 5.0% active ingredient with a dustingpowder as hereinbefore described, and in solutions containing from about0.01 to about 5.0% active ingredient with deodorized kerosene foraerosol applications.

It will of course be appreciated that the conditions encountered whenapplying the method and formulations of this invention to actualpractice can vary widely. Included among the variables that may beencountered are the degree of infestation by the pests, the particularpest to be controlled, the particular situs being treated, the age ordegree of development of animals or plants, the prevailing weatherconditions, such as temperature, relative humidity, rainfall, dews, andso forth.

The compounds of Formula I are effective pesticides that can be used tocontrol invertebrate pests in agri culture, in industry, and around thehome. The compounds have been found to be active against invertebrateanimals of the Phylum Arthropoda, illustratively Class Insecta, forexample, order Coleoptera, more specifically, the cotton boll weevil(Anthonomus grandis Boheman), the confused flour beetle (Triboliumconfusum Jacquelin de Val), and the Mexican bean beetle (.Epilachnavarivestis Mulsant), order Diptera, more specifically, the housefly(Musca domestica Linnaeus), order Orthoptera, more specifically, thehouse cricket (Acheta domesticus Linnaeus), and the German cockroach(Blatella germanica Linnaeus), and order Lepidoptera, more specifically,the Southern armyworm (Prodenia eridanta Cramer), and Class Arachnida,for example, order Acarina, more specifically, the two-spotted spidermite (Tetranychus urticae Koch).

Efficacy against invertebrate pests has been demonstrated atconcentrations of 1000, 500, 100, 50, and even 10 ppm depending upon thespecific insect or mite used. Some invertebrate animal pests will bemore sensitive to the compounds than others, and others might be quiteresistant. In general, the compounds of Formula I are used atconcentrations ranging from about 30 to about 6000 ppm.

' Compounds of the invention have also shown activity against parasiticworms, e.g., Nematospiroides dubius and Syphacia obvelata. The compounda,a,a-trifluorom-toluoyl chloride phenylhydrazone being particularlyeffective therefor.

I claim:

1. A method of combatting arthropod pests which comprises contacting thepests with an effective antiarthropodal amount of an(a-fluoroalkyl)benzoyl chloride phenylhydrazone having the structuralformula:

-F alkyl wherein a-F alkyl is an a-fluoroalkyl group of from 1 to 3carbon atoms, inclusive; n is the integer 2 or 3; X is halogen, alkyl offrom i to 6 carbon atoms, inclusive, a-F alkyl, or nitro; Y is halogen,alkyl of from 1 to 6 carbon atoms, inclusive, a F,,alkyl, or nitro; n isan integer from to 3, inclusive; and m is an integer from 0 to 3,inclusive; the sum of n m being not more than 5, the sum of carbon atomsin alkyl substituents being not more than 15, there being no more thanone nitro group in the molecule, and no more than two a-F alkyl groupson any one benzene ring or three total.

2. The method according to claim 1 wherein the compound isa,a,a-trifluoro-m-toluoyl chloride phenylhydrazone.

3. The method according to claim 1 wherein a-F alkyl is trifluoromethyl.

4. The method according to claim 3 wherein the trifluoromethyl group isin the meta position.

5. The method according to claim 4 wherein n is zero.

6. An anti-arthropodal composition comprising a dispersible carrier andan effective anti-arthropodal amount of an (oz-fluoroalkyUbenzoylchloride phenylhydrazone having the structural formula:

OL- F al kyl i F C=N- N wherein a-F alkyl is an a-fluoroalkyl group offrom 1 to 3 carbon atoms, inclusive; n is the integer 2 or 3;

14 X is halogen, alkyl of from 1 to 6 carbon atoms, inclusive, a-Falkyl, or nitro; Y is halogen, alkyl of from 1 to 6 carbon atoms,inclusive, ct-F alkyl, or nitro; n is an integer from O to 3, inclusive;and m is an integer from 0 to 3, inclusive; the sum of n m being notmore than 5, the sum of carbon atoms in alkyl substituents being notmore than 15, there being no more than one nitro group in the molecule,and no more than two a-F alkyl groups on any one benzene ring or threetotal.

7. The composition according to claim 6 wherein the compositioncomprises surface active agents.

8. The composition according to claim 6 for controlling arthropod pestscomprising the specific compound a,a,a-trifluoro-m-toluoyl chloridephenylhydrazone.

9. The composition according to claim 6 wherein a-F alkyl istrifluoromethyl.

10. The composition according to claim 9 wherein the trifluoromethylgroup is in the meta position.

11. The composition according to claim 10 wherein n is zero.

12. The composition according to claim 7 wherein the dispersible carrieris a liquid.

13. The composition according to claim 7 wherein the dispersible carrieris a finely divided solid.

14. The composition according to claim 7 for combatting arthropod pestscomprising the specific compound a,a,a-trifluoro-m-toluoyl chloridephenylhydrazone.

15. The composition according to claim 7 wherein oz-F alkyl istrifluoromethyl.

16. The composition according to claim 15 wherein the trifluoromethylgroup is in the meta position.

17. The composition according to claim 16 wherein n is zero.

1. A METNOD OF COMBATTING ARTHROPOD PESTS WHICH COMPRESES CONTACTING THEPESTS WITH AN EFFECTIVE ANTI-ARTHROPODAL AMOUNT OF AN(A-FLUOROALKYL)BENZOYL CHLORIDE PHENYLHYDRAZONE HAVING THE STRUCTURALFORMULA:
 2. The method according to claim 1 wherein the compound isAlpha , Alpha , Alpha -trifluoro-m-toluoyl chloride phenylhydrazone. 3.The method according to claim 1 wherein Alpha -Fnalkyl istrifluoromethyl.
 4. The method according to claim 3 wherein thetrifluoromethyl group is in the meta position.
 5. The method accordingto claim 4 wherein n'' is zero.
 6. An anti-arthropodal compositioncomprising a dispersible carrier and an effective anti-arthropodalamount of an ( Alpha -fluoroalkyl)benzoyl chloride phenylhydrazonehaving the structural formula:
 7. The composition according to claim 6wherein the composition comprises surface active agents.
 8. Thecomposition according to claim 6 for controlling arthropod pestscomprising the specific compound Alpha , Alpha , Alpha-trifluoro-m-toluoyl chloride phenylhydrazone.
 9. The compositionaccording to claim 6 wherein Alpha -Fnalkyl is trifluoromethyl.
 10. Thecomposition according to claim 9 wherein the trifluoromethyl group is inthe meta position.
 11. The composition according to claim 10 wherein n''is zero.
 12. The composition according to claim 7 wherein thedispersible carrier is a liquid.
 13. The composition according to claim7 wherein the dispersible carrier is a finely divided solid.
 14. Thecomposition according to claim 7 for combatting arthropod pestscomprising the specific compound Alpha , Alpha , Alpha-trifluoro-m-toluoyl chloride phenylhydrazone.
 15. The compositionaccording to claim 7 wherein Alpha -Fnalkyl is trifluoromethyl.
 16. Thecomposition according to claim 15 wherein the trifluoromethyl group isin the meta position.
 17. The composition according to claim 16 whereinn'' is zero.